Fluorinated cyclobutenyl alkyl ether copolymers

ABSTRACT

1. A HIGHLY FLUORINATED POLYMER OF THE FORMULA:   -((PEPFLUOROCYCLOBUTYLENE)X-(RT-O-RF&#39;&#39;)Y)N-I   WHEREIN RF AND RF&#39;&#39; ARE STRAIGHT CHAIN PERFLUOROALKYLENE GROUPS OR PERFLUOROOXALKYLENE GROUPS HAVING A COMBINED NUMBER OF CARBON ATOMS TOTALING FROM 3 TO 20, N IS A NUMBER FROM 2 TO 10,000 REPRESENTING THE DEGREE OF POLYMERIZATION AND THE RATIO OF X:Y RANGES FROM 0.001:1 TO 1000:1.

United States Patent ABSTRACT OF THE DISCLOSURE V Disclosed are highly fluorinated polymers of the for:

In the above formula, R, and R, are straight chain per- I fluoroalkylene groups or perfluorooxaalkylene having a combined number of carbon atoms totaling from 3 to 20, n is a number of from 2 to 10,000 representing the degree of polymerization and the ratio of xzy ranges from 0.001 :1 to 1000: 1. The polymers are thermally stable and flexible. In addition they contain double bonds as crosslinking sites.

BACKGROUND OF THE INVENTION Perfluorinated cyclobutadiene polymers have been made. We report their preparation in co-pending application S.N. 869,338, filed Oct. 24, 1969. These polymers have good thermal stability, but at high molecular weights they are inflexible. Likewise, polymers of perfluorinated ethers are reported in US. Pat. 3,505,411. These polyethers are flexible, but because of their high chemical stability are difiicult to crosslink by normal chemical methods. This invention combines the two systems in such a way that flexible polymers result containing double bonds which can act as crosslinking sites.

SUMMARY OF THE INVENTION The present invention comprises highly fluorinated polymers of the formula:

and a method for their preparation. In the above formula, Rf and R, are straight chain perfluoroalkylene or perfluorooxaalkylene having a combined number of carbon atoms of from 3 to 20, n is a number of from 2 to 10,000 representing the degree of polymerization and the ratio of any ranges from 0.001:1 to 1000:1.

DETAILED DESCRIPTION The polymers are prepared by a coupling type polymerization in which mercury and ultraviolet light are employed as reaction promoters. The reaction time may range from 1 hour to 6 months or more depending on the degree of polymerization desired. The reaction temperature may vary from 30 C. to 250 C. with a temperature of from 20 to 150 C. being preferred.

The monomeric materials are iodine terminated in order for the coupling reaction to proceed. The general reaction is set out in equation (I).

Patented Oct. 8, 1974 groups or perfluorooxaalkylene groups selected so that w .the total numb er of carbon atoms in the IRg '0 R1'I group ranges from 3 to 20. Specific examples of R, and R are perfluo rinated methyl, propyl, pentyl, decyl, dodecyl, tetradecyl and hexadecyl. The Rf and R, groups may independently be perfluorooxaalkylene examples of which are 2 2 2)a, 2)3 Z 5, (CF O(CF 1 The preferred polymers of the instant invention are those in which n is a number from 2 to 1,000, the comb e nu of carbo o s nRaanslRii. is from 3 to 11 and the ratio of any ranges from 1:5 to 5:1. When a liquid or rubbery polymer is desired, the, 1:5 ratio is The iodine terminated perfiuoro cyclobutene is prepared as set out in co-pending application 869,338. The iodine terminated ether may be prepared by the process disclosed in US. Pat. 3,505,411. Iodine terminated polyethers are also prepared by reacting a difunctional perfluoroacetyl fluoride with tetrafluoro ethylene in the presence of potassium fluoride and iodine. This preparation is indicated by equation (2) F F F f F F F IC-C-OC0FzCO-C-CI F F F F F F g In the above reaction n is a number from 1 to 14 thus providing a diether having up to 20 carbon atoms.

A method for preparing iodine terminated monoethers is represented by equation (3) (a) 0O-Ag 1 (cF9- -0 om) 1 2AgI 200,

In the above equation, m+n is equal to from 3 to 20.

The invention is further illustrated by the following examples.

EXAMPLES 1-5 In each of the following examples, polymers were prepared by reacting perfiuoro 3,4 diiodocyclobutene with perfiuoro 1,11 diiodo 3,9 dioxaundecane to form a polymer of the formula:

The reaction was carried out in a glass pressure vessel containing excess elemental mercury. In each run was employed as solvent. The reaction mass was irradiated with ultraviolet light while being cooled to 30 to 40 C. with a stream of air. After the reaction had gone to completion, as indicated by the presence of black mercuric iodide, the reaction mixture was centrifuged, with the freon soluble portion of the polymer being decanted oif, leaving the mercuric iodide and insoluble portion of the polymer behind. Then the soluble portion of the polymer was washed with aqueous potassium iodide. The solvent was evaporated to recover the polymer and the insoluble portion purified by vacuum subliming the mercury and mercury iodides from the polymer.

3 4 I The ratio of perfiuorobutene moieties to perfluoroether 3. The polymer of claim 2 wherein the ratio of xzy Vmoietiesflin the polymer are modified by adjusting the ranges from 1:5 t o 5:1.

4. The polymer of claim 3 wherein the combined number of carbon atoms in R; and R; totals 3 to 11. 5 5. The polymer of claim 1 wherein R; and Rf are perfluorinated methyl, propyl, pentyl, decyl, dodecyl, tetradecyl orhexadecyl. i

6. The polymer of claim 1 wherein 'R and R are each selected from (CF 'O'(CF stoichiometry. The degree of polymerization in each run was determined by iodine end group analysis.

"The reactants and products of examples '1-5 are set out in Table I. v v y p v Due to their high fluorine content these compounds exhibit good thermal and oxidation resistance. The liquid polymers are useful as hydraulic fluids for high temperature apphcatlons such as breaking systems. The SOlld --(CF O-( 2) 5- polymers can be used to form ablatlves and gaskets for uses in which stability is essential. or -(CF 0(CF TABLE I Reaction parameters Product parameters a Degree of Y Ratio Mercury Solvent, Time, polymeri- Cyelobutene (X) Ether(Y) X:Y gm. ml. hours zation Physical properties :1 10.0 50 309 n=-35 -Soi't solid. :5 10.0 76 n=-350 Mobile nonvolatile liquid. :2 10.0 -25 112 n=-300 D0. 1 10.1 25 19s n=-300 D0. 1 10.2 25 177 n=-l60 Do.

We claim: 25 7. The polymers of claim 1 wherein R: is 1. A highly fluorinated polymer of the formula: F F f F F -CC- and R! is CF:-0-CC- F F A F F l' I References Cited 7 L E V J UNITED STATES PATENTS Y 3,505,411 4/1970 Rice 260615 BF 3,657,306 4/1972 Murray 260611 RX 3,697,564 10/ 1972 Anello et a1 260-911 RX wherein R; and R, are straight chain perfluoroalkylene groups or perfluorooxalkylene groups having a combined HOWARD M ARS, Primary Examiner number of carbon atoms totaling from 3 to 20, n is a number from 2 to 10,000 representing the degree of po- MORGENSTERN Asslstant Examlnel' llygggrilaatlon and the ratio of xzy ranges from 0.001:1 to 40 Us. Cl. X'R.

2. The polymer of claim 1 wherein n is a number from 204158; 25211, 52 A, 54; 260-823 #23353? UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,840,603 Dated October a, 1974 lnvent0r(S) I Richard W. Anderson & Hughie R. Fr'ick 7 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

F" Column 1, line 64, delete "equation (I) and insert "1 "equation (l)--; I

Column 1, line 65, delete (1)" and insert -(l)--;

Column 1, line 66, delete "XI and insert --xI;--

Column 1, line 68, delete "VI"- andv insert -v yI,-

Column 2, line 8, delete the entire line and insert are (CF -0- (CF (CF -0- (CF and,

Column 2, line 30, delete "CH and insert CF Column 2, line 33, at the end of theformula insert --+KI--;

Column 2, line 40, change the formula to read H I2 Ag-O- CF2 0 CF C-C-Ag n m A Column 3, line 30, at the beginning of the formula insert --I--;' Column 3, line 36, correct'the spelling of the third word to read -perfluorooxaalkylene-.

L- Signed and sealed this 21st day of January 1975.

(SEAL) Attest: MCCOY M. GIBSON. J R. C. MARSHALL DANN Attesting Officer Commissioner of Patents 

1. A HIGHLY FLUORINATED POLYMER OF THE FORMULA: 